U.S. patent number 4,154,699 [Application Number 05/855,875] was granted by the patent office on 1979-05-15 for manufacture of a titanium-containing component for catalysts of the ziegler-natta type.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to James F. R. Jaggard, Heinz Mueller-Tamm, Johann Nickl, Hans Schick.
United States Patent |
4,154,699 |
Mueller-Tamm , et
al. |
May 15, 1979 |
Manufacture of a titanium-containing component for catalysts of the
Ziegler-Natta type
Abstract
A process for the manufacture of a titanium-containing component
of a catalyst for the polymerization of monoolefins by the
Ziegler-Natta method by milling (a) a particular
titanium-containing compound, viz. a titanium trichloride/aluminum
trichloride complex and (b) a particular ester with one another, in
which process (1) a vibratory ball mill producing a particular
milling acceleration is used, (2) the mill is first charged with
the titanium-containing compound (a) and may or may not then be run
for some time in the absence of diluents, (3) while milling, the
ester (b) is added at a particular rate, continuously or in small
portions, and in the absence of diluents, thereafter (4) the grist
is brought to an elevated temperature, while milling, and is kept
at this temperature until from 5 to 85% of the aluminum trichloride
originally present in a bonded form in the titanium-containing
compound (a) have been eliminated from the said compound (a), after
which (5) if appropriate, the product obtained in accordance with
(4) is washed with a hydrocarbon and dried, and then (6) the
product obtained in accordance with (4) or in accordance with (5)
is milled for a certain length of time at a low temperature in the
absence of a diluent. Polyolefins of high stereoregularity can be
obtained in a high specific yield by means of the catalyst
component manufactured according to the invention.
Inventors: |
Mueller-Tamm; Heinz
(Ludwigshafen, DE), Schick; Hans (Mannheim,
DE), Jaggard; James F. R. (Ludwigshafen,
DE), Nickl; Johann (Bad Duerkheim, DE) |
Assignee: |
BASF Aktiengesellschaft
(DE)
|
Family
ID: |
5996702 |
Appl.
No.: |
05/855,875 |
Filed: |
November 30, 1977 |
Foreign Application Priority Data
|
|
|
|
|
Dec 24, 1976 [DE] |
|
|
2658939 |
|
Current U.S.
Class: |
502/105; 526/142;
526/159 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 10/00 (20130101); C08F
4/651 (20130101) |
Current International
Class: |
C08F
10/00 (20060101); C08F 004/64 () |
Field of
Search: |
;252/429B,429A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Garvin; Patrick
Attorney, Agent or Firm: Keil & Witherspoon
Claims
We claim:
1. A process for the manufacture of a titanium-containing component
of a catalyst for the homopolymerization and copolymerization of
.alpha.-monoolefins of 3 to 6 carbon atoms by the Ziegler-Natta
method, by milling together
(a) a titanium-containing compound of the general formula
where n is a number from 0.01 to 1, and
(b) an ester of a total of 2 to 34 carbon atoms, which has the
general formula ##STR3## where R.sup.1 is (I) alkyl of 1 to 16
carbon atoms or (II) phenylalkyl of a total of 7 to 23 carbon
atoms, up to 5 hydrogen atoms of the phenyl radical being
unsubstituted or substituted by alkyl of 1 to 5 carbon atoms, and
R.sup.2 is (I) hydrogen, (II) alkyl of 1 to 18 carbon atoms, (III)
phenylalkyl of a total of 7 to 23 carbon atoms, up to 5 hydrogen
atoms of the phenyl radical being unsubstituted or substituted by
alkyl of 1 to 5 carbon atoms, (IV) phenyl or (V) alkylphenyl of a
total of 7 to 23 carbon atoms, up to 5 hydrogen atoms of the phenyl
radical being unsubstituted or substituted by alkyl of 1 to 5
carbon atoms, individual radicals R.sup.2 being identical or
different when more than one is present, wherein
(1) a vibratory ball mill producing a milling acceleration of from
30 to 80 m.sec..sup.-2 is employed,
(2) the mill is first charged with the titanium-containing compound
(a), after which it may or may not be operated in the absence of a
diluent at from -50 to +100.degree. C. over a period of from
50.degree. to 100 hours, then
(3) whilst milling at a grist temperature of from -50.degree. to
+80.degree. C. an amount of the ester (b) which corresponds to a
molar ratio of aluminum in the titanium-containing compound (a) to
ester (b) of from 1:5 to 1:0.5 is added continuously or at
intervals, in the absence of a diluent, at a rate of from 0.01 to
200 ml/min per 2.5 kg of titanium-containing compound (a),
thereafter
(4) whilst being milled, the grist is brought to from +10.degree.
to +100.degree. C. and is kept in this temperature range until from
5 to 85% of the aluminum trichloride originally present in a bonded
form in the titanium-containing compound (a) has been eliminated
from the latter, after which
(5) is desired, the product obtained in accordance with (4) is
washed with at least 0.6 times its amount by weight of a
hydrocarbon which is liquid at standard temperature and pressure
and boils below 150.degree. C. at standard pressure and is dried,
and then
(6) the product obtained in accordance with (4) or (4) and (5) is
milled, in the absence of diluents, for a period of from 5 to 60
minutes at from -50.degree. to -10.degree. C.
2. A process as claimed in claim 1, wherein a vibratory ball mill
providing a milling acceleration of 45 to 55 m.sec.sup.-2 is
employed.
3. A process as claimed in claim 1, wherein the vibratory ball mill
is operated in the absence of a diluent at from -30.degree. to
+50.degree. C., over a period of from 2 to 20 hours in step
(2).
4. A process as claimed in claim 1, wherein, whilst milling at a
grist temperature of from -30.degree. to +60.degree. C., an amount
of the ester (b) which corresponds to a molar ratio of aluminum in
the titanium-containing compound (a) to ester (b) of from 1:2 to
1:0.7 is added at a rate of from 10 to 80 ml/min per 2.5 g of
titanium-containing compound (a) in step (3).
5. A process as claimed in claim 1, wherein, whilst being milled in
step (4), the grist is brought to from +20.degree. to +60.degree.
C. and is kept in this temperature range until from 10 to 70% of
the aluminum trichloride originally present in a bonded form in the
titanium-containing compound (a) has been eliminated from the
latter.
6. A process as claimed in claim 1, wherein step (5) is performed
and the liquid hydrocarbon used in step (5) boils below 100.degree.
C. at standard pressure.
7. A process as claimed in claim 1, wherein the product is milled
in step (6) for a period of from 10 to 30 minutes at from
-40.degree. to -20.degree. C.
8. A process as claimed in claim 1, wherein, for the
titanium-containing compound (a), n is a number from 0.1 to
0.4.
9. A process as claimed in claim 1, wherein the ester (b) has the
formula
where R.sup.1 is alkyl of 1 to 8 carbon atoms or phenylalkyl of 7
to 14 carbon atoms and R.sup.2 is hydrogen, alkyl of 1 to 12 carbon
atoms, phenyl or alkylphenyl or phenylalkyl of a total of 7 to 14
carbon atoms, the ester containing a total of 2 to 18 carbon
atoms.
10. A process as claimed in claim 1, wherein the ester (b) has the
formula ##STR4## where R.sup.1 has the meaning given in claim 9 and
R.sup.2 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl or
phenylalkyl or alkylphenyl of a total of 1 to 14 carbon atoms,
individual radicals R.sup.2 being identical or different, the ester
containing a total of 4 to 18 carbon atoms.
Description
The present invention relates to a process for the manufacture of a
titanium-containing component of a catalyst for the
homopolymerization and copolymerization of .alpha.-monoolefins of 3
to 6 carbon atoms by the Ziegler-Natta method, in which
(A) A TITANIUM-CONTAINING COMPOUND OF THE GENERAL FORMULA
Where n is a number from 0.01 to 1 and
(B) AN ESTER OF A TOTAL OF FROM 2 TO 34 CARBON ATOMS, WHICH HAS THE
GENERAL FORMULA ##STR1## where R.sup.1 is (I) alkyl of 1 to 16
carbon atoms or (II) phenylalkyl of a total of 7 to 23 carbon
atoms, up to 5 hydrogen atoms of the phenyl radical being
unsubstituted or substituted by alkyl of 1 to 5 carbon atoms, and
R.sup.2 is (I) hydrogen, (II) alkyl of 1 to 18 carbon atoms, (III)
phenylalkyl of a total of 7 to 23 carbon atoms, up to 5 hydrogen
atoms of the phenyl radical being unsubstituted or substituted by
alkyl of 1 to 5 carbon atoms, (IV) phenyl or (V) alkylphenyl of a
total of 7 to 23 carbon atoms, up to 5 hydrogen atoms of the phenyl
radical being unsubstituted or substituted by alkyl of 1 to 5
carbon atoms, individual radicals R.sup.2 being identical or
different when more than one is present, are milled with one
another.
A plurality of processes of this type have been disclosed; in the
main, the object of these processes is to obtain
titanium-containing components which, after activation with an
organo-aluminum compound or the like--give catalysts which, when
used for polymerizing .alpha.-olefins, give high specific yields of
poly-.alpha.-olefins and/or give poly-.alpha.-olefins with a
relatively high proportion of stereoregular polymer.
The conventional processes have achieved substantial success.
However, it is a certain disadvantage that the titanium-containing
components, when used in catalysts of the Ziegler-Natta type which
are employed for the polymerization of .alpha.-olefins, either give
polymers which have a relatively high stereoregularity
(isotacticity give only relatively low specific yields of the
polymers, or vice versa.
It is an object of the present invention to provide a process of
the type defined at the outset by means of which it is possible to
obtain titanium-containing components which are free from the above
disadvantage, or suffer from it to a substantially reduced
degree.
We have found that this object is achieved by working under
particular physical milling conditions, bringing the starting
materials together in a specific manner, milling them with one
another until a particular critical range is reached, and
after-treating the resulting intermediate of the desired
titanium-containing component in a specific manner.
Accordingly, the present invention relates to a process for the
manufacture of a titanium-containing component of a catalyst for
the homopolymerization and copolymerization of .alpha.-monoolefins
of 3 to 6 carbon atoms by the Ziegler-Natta method, by milling
together
(a) a titanium-containing compound of the general formula
where n is a number from 0.01 to 1, especially from 0.1 to 0.4,
and
(b) an ester of a total of 2 to 34, especially 2 to 18, carbon
atoms, which has the general formula ##STR2## where R.sup.1 is (I)
alkyl of 1 to 16, especially of 1 to 8, carbon atoms or (II)
phenylalkyl of a total of 7 to 23, especially of 7 to 14, carbon
atoms, up to 5 hydrogen atoms of the phenyl radical being
unsubstituted or substituted by alkyl of 1 to 5 carbon atoms, and
R.sup.2 is (I) hydrogen, (II) alkyl of 1 to 18, especially of 2 to
12, carbon atoms, (III) phenylalkyl of a total of 7 to 23,
especially of 7 to 14, carbon atoms, up to 5 hydrogen atoms of the
phenyl radical being unsubstituted or substituted by alkyl of 1 to
5 carbon atoms, (IV) phenyl or (V) alkylphenyl of a total of 7 to
23, especially of 7 to 14, carbon atoms, up to 5 hydrogen atoms of
the phenyl radical being unsubstituted or substituted by alkyl of 1
to 5 carbon atoms, individual radicals R.sup.2 being identical or
different when more than one is present, wherein
(1) a vibratory ball mill producing a milling acceleration of from
30 to 80, especially from 45 to 55, m.sec..sup.-2 is employed,
(2) the mill is first charged with the titanium-containing compound
(a), after which it may or may not be operated in the absence of a
diluent at from -50.degree. to +100.degree. C., especially from
-30.degree. to +50.degree. C., over a period of from 0.5 to 100
hours, especially from 2 to 20 hours, then
(3) whilst milling at a grist temperature of from -50.degree. to
+80.degree. C., especially from -30.degree. to +60.degree. C., an
amount of the ester (b) which corresponds to a molar ratio of
aluminum in the titanium-containing compound (a) to ester (b) of
from 1:15 to 1:0.05, especially from 1:2 to 1:0:7, is added
continuously or at intervals, in the absence of a diluent, at a
rate of from 0.01 to 200, especially from 10 to 80, ml/min per 2.5
kg of titanium-containing compound (a), thereafter
(4) whilst being milled, the grist is brought to from +10.degree.
to +100.degree. C., especially from +20.degree. to +60.degree. C.,
and is kept in this temperature range until from 5 to 85%,
especially from 10 to 70%, of the aluminum trichloride originally
present in a bonded form in the titanium-containing compound (a)
has been eliminated from the latter, after which
(5) is desired, the product obtained in accordance with (4) is
washed with at least 0.6 times its amount by weight of a
hydrocarbon which is liquid at standard temperature and pressure
and boils below 150.degree. C., especially below 100.degree. C., at
standard pressure and is dried, and then
(6) the product obtained in accordance with (4) or (4) and (5) is
milled, in the absence of diluents, for a period of from 5 to 60
minutes, especially from 10 to 30 minutes, at from -50.degree. to
-10.degree. C., especially from -40.degree. to -20.degree. C.
The following should be noted with respect to the materials used in
the new process.
The titanium-containing compounds (a) having the stated general
formula are the relevant conventional compounds, for example those
obtainable by co-crystallization TiCl.sub.3 and AlCl.sub.3 or
reducing TiCl.sub.4 by means of aluminum or mixtures of aluminum
and titanium. Co-crystallized products of the formula
TiCl.sub.3.1/3AlCl.sub.3 are particularly suitable. The appropriate
titanium-containing compounds (a) are commercially available, so
that more detailed comments are superfluous.
Suitable esters (b) having the stated general formula are again the
relevant conventional compounds conforming to this formula,
especially those where R.sup.1 is methyl, ethyl, propyl, n-butyl,
n-pentyl, i-pentyl, n-hexyl or benzyl and R.sup.2 is hydrogen or
methyl, ethyl, n-propyl, n-butyl, n-pentyl, i-pentyl, n-hexyl,
n-heptyl, n-octyl, phenyl, benzyl, 1-phenylethyl, 2-phenylethyl,
3-phenylpropyl, 4-phenylbutyl or 5-phenylpentyl.
Specific examples of very suitable esters (b) are ethyl acetate,
butyl acetate, ethyl n-butyrate and butyl acrylate.
Other particularly suitable esters (b) are ethyl propionate, ethyl
n-valerate, ethyl phenylacetate, ethyl 3-phenylpropionate, ethyl
4-phenylbutyrate and butyl methacrylate.
The liquid hydrocarbon to be used on step (5) can be a hydrocarbon
of the type which is conventionally brought into contact with
titanium-containing components for catalysts of the Ziegler-Natta
type, without detriment to the catalyst or to its
titanium-containing component, for example in the polymerization of
.alpha.-monoolefins. Examples of suitable hydrocarbons are
pentanes, hexanes, heptanes, gasolines and cyclohexane.
The process according to the invention is very simple to carry out
and does not require any explanation to those skilled in the art.
At most, what requires mention is that the degree of partial
elimination of the aluminum chloride from the titanium-containing
compound (a), which degree is critical in step (4) can easily be
ascertained by taking a sample of the grist periodically, washing
it--for example with the hydrocarbon to be used in step (5)-- and
drying it and analyzing the resulting solid. Step (5) will
expediently be carried out if, for example, the grist from step (4)
is sticky or contains relatively large amounts of ester (b).
The titanium-containing components for catalysts of the
Ziegler-Natta type, manufactured by the process of the invention,
can be employed in the relevant conventional manner in the
polymerization of .alpha.-olefins, i.e. these titanium components
are in general used together with an organo-metallic activator,
especially with an aluminum-alkyl compound of the formula
Al(alkyl).sub.3 or ClAl(alkyl).sub.2, where alkyl is of one to
eight carbon atoms, and above all together with triethylaluminum or
diethyl-aluminum chloride.
Particularly good results are obtained in the dry polymerization of
.alpha.-olefins, i.e. the polymerization in the absence of liquid
auxiliary media; however, polymerization in the presence of such
media can also be carried out with good success. The molecular
weight can be adjusted by means of the conventional regulators,
especially hydrogen. Suitable .alpha.-olefins to polymerize are
those of three of six carbon atoms, especially propylene, 1-butene
and 4-methyl-1-pentene.
EXAMPLE 1
Manufacture of the titanium-containing component
The starting compounds are
(a) a titanium compound of the formula TiCl.sub.3.1/3AlCl.sub.3
and
(b) ethyl n-valerate.
Milling is carried out in a vibratory ball mill having a useful
volume of 10 liters.
In other respects the procedure followed is that:
(1) the mill is operated with a milling acceleration of 53
m.sec.sup.-2,
(2) the mill is initially charged with 2.4 kg of the
titanium-containing compound (a) and is operated in the absence of
diluents at 15.degree. C. for a period of 14 hours, then
(3) whilst milling at a grist temperature of -24.degree. C., the
amount of the ester (b) which corresponds to a molar ratio of
aluminum in the titanium-containing compound (a) to ester (b) of
1:1 is added continuously at a rate of 48 ml/min per 2.5 kg of
titanium-containing compound (a), in the absence of diluents,
thereafter
(4) whilst milling, the grist is brought to 40.degree. C. and is
kept near this temperature until 24% of the aluminum trichloride
originally present in a bonded form in the titanium-containing
compound (a) has been eliminated from the said compound, after
which
(5) the product obtained in accordance with (4) is washed with 5.3
times its amount by weight of hexane and dried under argon and
then
(6) the product obtained in accordance with (5) is milled for a
period of 10 minutes at -30.degree. C. in the absence of
diluents.
Polymerization by means of the titanium-containing component
1.0 gram of the titanium-containing component and 1.98 grams of
diethyl-aluminum chloride are introduced into a 2 liter stirred
flask which is charged with 1.5 liters of dry heptane. The
polymerization is then carried out for a period of 5 hours whilst
stirring, under a propylene pressure of 1 bar at 60.degree. C., the
pressure and temperature being regulated to keep them constant;
thereafter the polymerization is stopped by adding 20 ml of
methanol and the suspension medium is removed by distillation.
192 g of polypropylene are obtained, corresponding to a
productivity of 273 parts by weight of polypropylene per part by
weight of titanium-containing compound (a), calculated as
TiCl.sub.3. The polypropylene contains 1.5 percent by weight of
material soluble in boiling n-heptane.
EXAMPLE 2
Manufacture of the titanium-containing component
The starting compounds are
(a) a titanium compound of the formula TiCl.sub.3.1/3AlCl.sub.3
(commercial finely milled material) and
(b) butyl methacrylate.
Milling is carried out in a vibratory mill having a useful volume
of 10 liters.
In other respects the procedure followed is that:
(1) the mill is operated with a milling acceleration of 50
m.sec.sup.-2,
(2) the mill is initially charged with 2.4 kg of the
titanium-containing compound (a), then
(3) whilst milling at a grist temperature of -26.degree. C., the
amount of the ester (b) which corresponds to a molar ratio of
aluminum in the titanium-containing compound (a) to ester (b) of
1:1 is added in discrete portions at a rate of 58 ml/min per 2.5 kg
of titanium-containing compound (a), in the absence of diluents,
thereafter
(4) whilst milling, the grist is brought to 40.degree. C. and is
kept near this temperature until 12% of the aluminum trichloride
originally present in a bonded form in the titanium-containing
compound (a) has been eliminated from the said compound, after
which
(5) the product obtained in accordance with (4) is washed with 5.5
times its amount by weight of n-hexane and dried and then
(6) the product obtained in accordance with (5) is milled for a
period of 12 minutes at -30.degree. C. in the absence of
diluents.
Polymerization by means of the titanium-containing component
The process is carried out using a stirred reactor of 0.8 m.sup.3
capacity, under a propylene pressure of 28 bars, which is
maintained continuously by a regulating system, and using an amount
of hydrogen of 90 liters (S.I.P.)/h, at a reaction temperature of
70.degree. C., regulated continuously to keep it constant, and in
the absence of solvents and diluents, in a bed of 280 kg of small
particles of propylene polymer. The reactor is operated
continuously, with 12 g/h of the titanium-containing component and
42 g/h of (C.sub.2 H.sub.5).sub.2 AlCl being introduced separately
from one another.
The reactor produces polypropylene in the form of small particles,
of average size about 0.2 mm; this product contains 32 ppm, by
weight, of titanium and 4.4% by weight of material soluble in
boiling n-heptane, and has an intrinsic viscosity of 2.8 dl/g.
EXAMPLE 3
Manufacture of the titanium-containing component
The starting compounds are
(a) a titanium compound of the formula TiCl.sub.3.1/3AlCl.sub.3
and
(b) ethyl 4-phenylbutyrate
Milling is carried out in a vibratory ball mill having a useful
volume of 10 liters.
In other respects the procedure followed is that:
(1) the mill is operated with a milling acceleration of 53
m.sec.sup.-2,
(2) the mill is initially charged with 2.4 kg of the
titanium-containing compound (a) and is operated in the absence of
diluents at 15.degree. C. for a period of 15 hours, then
(3) whilst milling at a grist temperature of -26.degree. C., the
amount of the ester (b) which corresponds to a molar ratio of
aluminum in the titanium-containing compound (a) to ester (b) of
1:1 is added continuously at a rate of 58 ml/min per 2.5 kg of
titanium-containing compound (a), in the absence of diluents,
thereafter
(4) whilst milling, the grist is brought to 40.degree. C. and is
kept near this temperature until 12% of the aluminum trichloride
originally present in a bonded form in the titanium-containing
compound (a) has been eliminated from the said compound, after
which
(5) the product obtained in accordance with (4) is washed with 5.2
times its amount by weight of hexane and dried under argon and
then
(6) the product obtained in accordance with (5) is milled for a
period of 12 minutes at -30.degree. C. in the absence of
diluents.
Polymerization by means of the titanium-containing component
1.0 gram of the titanium-containing component and 1.67 grams of
diethyl-aluminum chloride are introduced into a 2 liter stirred
flask which is charged with 1.5 liters of dry heptane. The
polymerization is then carried out for a period of 5 hours whilst
stirring, under a propylene pressure of 1 bar at 60.degree. C., the
pressure and temperature being regulated to keep them constant;
thereafter the polymerization is stopped by adding 20 ml of
methanol and the suspension medium is removed by distillation.
159 g of polypropylene are obtained, corresponding to a
productivity of 268 parts by weight of polypropylene per part by
weight of titanium-containing compound (a), calculated as
TiCl.sub.3. The polypropylene contains 1.6 percent by weight of
material soluble in boiling n-heptane.
* * * * *